CN1024771C - Stretched polypropene film - Google Patents

Abstract

To obtain the title film in which losses of transparency and rigidity are small and which has excellent see-through. A process for producing polypropylene, which comprises preliminarily polymerizing 3-methylbutene-1 in the presence of a catalyst system, the amount of the 3-methylbutene-1 preliminarily polymerized being 0.1 to 100 g per gram of the solid titanium catalyst, and thereafter, polymerizing propylene or copolymerizing propylene and an alpha-olefin in the presence of the catalyst used in the preliminary polymerization to such an extent that the amount of the monomer or monomers polymerized is from 1,000 to 100,000 times the amount of the 3-methylbutene-1 preliminarily polymerized.

Description

Stretched polypropene film

The present invention relates to a kind of have excellent transparency can stretched polypropene film, its transparency and rigidity variation hardly, this film is to obtain by the polypropylene that simple tension at least contains 3-methyl butene-1 polymer of specified quantitative.

People know that many acrylic polymers and propylene/alpha-olefins copolymer have very high directionality index, and many their production methods.

People also know, can produce acrylic polymers and propylene/alpha-olefins copolymer under very high catalyst efficiency.

In order to improve the properties of transparency or the transparency of acrylic polymers and propylene/alpha-olefins copolymer, people have made many trials.For example, Japanese patent application publication No. 80329/1983 discloses and a kind of Sodium Benzoate (as nucleator) has been dispersed in the polypropylene to improve its transparent specific process.Japanese patent application publication No. 12460/1980 discloses a kind of method, and with 1,3,2,4-two (methyl benzal) sorbierite is mixed in crystalline polypropylene, increases its transparency.

The corresponding BP 1104665 of Japanese patent application publication No. 32430/1970() production method of the solid polymer moulding compound of propylene-containing copolymer is disclosed, described composition contains 55%(weight at least) the propylene chain link, the chain link of second component is the straight chain 1-alkene that contains 4 to 18 carbon atoms, its amount is at most 35%(weight), and be dispersed in fully in the polymer unit of composition the 3rd component, it is the homopolymers of alpha-olefin, crystalline melting point is more than 180 ℃, and latter's content is at most 10%(weight).This method comprises translates propylene, second component catalyst with the 3rd component and solid and contacts, and this catalyst is to form with the transistion metal compound of the 4th to the 6th family of organo-metallic compound or metal hydride activation.This patent documentation points out that the transparency that generates composition is improved, and surpasses acrylic resin, points out 3-methylpentene-1,4 again simultaneously, 4-dimethyl pentene-1, and vinyl cyclohexane, 3-methyl butene-1 are especially suitable for use as the 3rd component.

U.S. Patent number 4551501 discloses the composition of the crystalline propene polymer with excellent transparency and rigidity, said composition comprises the mixture of polymers of the vinyl cycloalkane of crystalline polypropylene and at least 6 carbon atoms, contains the vinyl cycloalkane unit of 0.05 ppm by weight to 10000 ppm by weight.In the comparative example 4 to 6 of this patent, in the presence of titanium trichloride catalyst and diethyl aluminum, will allow the homopolymerization of a small amount of 3-methyl butene-1, then, allow a large amount of propylene homopolymerizations, generation contain the propylene copolymer of poly-(3-methyl-1-butene) (to every gram titanium trichloride) of 0.3 to 2 gram; Subsequently copolymer is mixed with Noblen, preparation contains the composition of 2 to 200 ppm by weight poly-(3-methyl-1-butene).From the table 3 of this patent as can be seen, the total light transmission of producing of composition is fabulous, still, and for the composition that in this patent working example 7, prepares with similar method, contain 7ppm poly-(vinyl cyclohexane), haze value, light scattering index (LSI) and gloss are relatively poor.

The purpose of this invention is to provide a kind of improved stretched polypropene film with excellent transparency energy.

According to the present invention, its objective is that polyacrylic method realizes by producing, this method comprises pre-poly 3 methyl butene 1 under the existence of the catalyst system that is formed by following component:

(A) contains magnesium, titanium, halogen and the polycarboxylate solid titanium catalyst component as principal component;

(B) organo-aluminum compound and

(C) is RnSi(OR by general formula ¹) _4-nThe organo-silicon compound of expression, wherein R and R ¹Representation hydrocarbyl, 0＜n＜4;

The amount of pre-poly 3 methyl butene 1 is 0.1 to 100 gram to every gram solid titanium catalyst, then, in the presence of the catalyst that in pre-collecting process, uses, polypropylene or be 1000 to 100000 times of amount of the 3-methyl butene-1 of pre-polymerization with propylene and alpha-olefin copolymer to the amount of monomer or polymerization single polymerization monomer.

From the angle of prior art, can have the film forming polypropylene of excellent transparency energy with said method production, this is unexpected.

The resulting stretched polypropene film of polymer that the objective of the invention is to contain by simple tension at least the 3-methyl-butene-1 of 1 to 1000 ppm by weight is realized.

The present invention will be described in detail as follows.

The present invention includes the polyacrylic method of producing, this method comprises pre-polymerization 3-methyl butene-1 under the existence of the catalyst system that is formed by following component,

(A) contains magnesium, titanium, halogen and the polycarboxylate solid titanium catalyst system as principal component;

(B) organo-aluminum compound and

(C) is by general formula R nSi(OR ¹) _4-nThe organo-silicon compound of expression, wherein R and R ¹Representation hydrocarbyl, 0＜n＜4;

The amount of the 3-methyl butene-1 of pre-polymerization is 0.1 to 100 gram to every gram solid titanium catalyst, then, the catalyst that in pre-collecting process, uses in the presence of polypropylene or with propylene and alpha-olefin copolymer to the amount of the monomer of monomer or pre-polymerization 1000 to 100000 times as the amount of the 3-methyl butene-1 of pre-polymerization.

The titanium catalyst component (A) that is used for catalyst system of the present invention contains magnesium, titanium, halogen and the polycarboxylate as principal component.

Titanium catalyst component A contains than the little magnesium halide of commercially available magnesium halide crystallite.Usually, its specific area is at least 3 meters ²/ gram is preferably about 30 to about 1000 meters ²/ gram, more preferably about 100 to 800 meters ²/ gram, and when at room temperature washing with hexane, its composition does not change basically.When using, during as silicon compound, aluminium compound or polyolefin,, will demonstrate high performance even the specific area of titanium catalyst component is lower than above-mentioned specific scope as inorganic or organic compound and so on diluent.Be preferably in the titanium catalyst component (A), the atomic ratio of halogen/titanium is about 5 to about 200, particularly about 5 to about 100; The mol ratio of electron donor/titanium is about 0.1 to about 10, particularly about 0.2 to about 6.The atomic ratio of magnesium/titanium is about 1 to about 100, particularly about 2 to about 50.Catalytic component (A) also can further contain other electron donor, metal, element, functional group or the like.

Titanium catalyst component (A) can be by making as magnesium compound (or magnesium metal), electron donor and titanium compound are in contact with one another; The compound of other reagent such as silicon, phosphorus and aluminium is talked about as desired and can also be used.

Titanium catalyst component (A) basically can by as utilize the described method of following Japanese patent application publication No. to produce; 108385/75,126590/75,20297/76,28189/76,64586/76,92885/76,136625/76,87489/77,100596/77,147688/77,104593/77,2580/78,40093/78,40094/78,135102/80,135103/81,811/81,11908/81,18606/81,83006/83,138705/83,138706/83,138707/83,138708/83,138709/83,138710/73,138715/83,23404/85,21109/86,37802/86,37803/86 and 152710/80.Producing the example of the certain methods of titanium catalyst component (A) will describe briefly.

(1) with the solid complex of solid magnesium compound or magnesium compound and electron donor and the titanium compound reaction that under reaction condition, is liquid.Before the reaction, electron donor and powdered auxiliary agent exist or non-existent situation under, magnesium compound or complex compound can be clayed into power, also can be in advance react with electron donor and/or reaction promoter such as organo-aluminum compound or halogen-containing silicon compound.In said process, electron donor will be used once at least.

(2) titanium and the liquid titanium compound of liquid form that will not have the magnesium compound of reducing power reacts in the presence of electron donor, is settled out solid titanium complex.

(3) product and the titanium compound with (2) reacts.

(4) product of (1) or (2) and electron donor and titanium compound are reacted.

(5) solid complex of solid magnesium compound or magnesium compound and electron donor and halogen, halogen compounds or aromatic hydrocarbons react.Before the reaction, magnesium compound or complex compound can be existed or do not exist and clay into power under the condition that titanium compound exists at electron donor and powdered auxiliary agent, also can be in advance and electron donor and/or reaction promoter such as organo-aluminum compound or the reaction of halogen-containing silicon compound.In said process, electron donor uses once at least.

(6) product of (1), (2), (3) or (4) is handled with halogen, halide or aromatic hydrocarbons.

(7) contact with titanium compound with polycarboxylate by contact the product that obtains with metal oxide, dialkyl magnesium and halogen-containing alcohol.

(8) magnesium compound reacts as organic acid magnesium salts, alkoxyl magnesium or aryloxy group magnesium and polycarboxylate, titanium compound and/or halogen-containing hydrocarbon.

In these methods, use the liquid halogenated titanium and after using titanium compound or what use halogenated hydrocarbons between the operating period is preferable.

Can using in the present invention, the electron donor of a component of titanium catalyst component (A) is a polycarboxylate.Preferable polycarboxylate is the compound that the skeleton by following chemical formulation constitutes:

Wherein, R ¹Representative replaces or unsubstituted alkyl, R ², R ⁵And R ⁶Represent hydrogen atom or replacement or unsubstituted alkyl, R ³And R ⁴Represent hydrogen atom or replacement or unsubstituted alkyl, preferably R ³And R ⁴In at least one is to replace or unsubstituted alkyl, and R ³And R ⁴Can interconnect.The alkyl of the replacement in the definition is the group that can contain hetero atom such as N, O or S, for example C-O-C, COOR, COOH, OH, SO in the above ₃H ,-C-N-C-or NH ₂

Particularly preferred dicarboxylic diester, wherein R at least ¹And R ²One of be the alkyl that contains 2 carbon atoms at least.

Preferred example with polycarboxylate of above-mentioned skeleton comprises polycarboxylate of aliphatic series, for example diethyl succinate, dibutyl succinate, the dimethyl succinic acid diethylester, Alpha-Methyl glutaric acid diisobutyl ester, malonic acid dibutylmethyl ester, diethyl malonate, ethyl malonic acid diethylester, diethyl isopropyl, the butylmalonic acid diethylester, phenyl ethyl malonate, ethyl diethylmalonate, allyl diethyl malonate, the diisobutyl diethyl malonate, the butylmalonic acid diethylester, phenyl ethyl malonate, the di-n-butyl diethyl malonate, dimethyl maleate, the maleic acid list is sad, diisooctyl maleate, diisobutyl maleate, the butyl diisobutyl maleate, the butyl diethyl maleate, Beta-methyl glutaric acid diisopropyl ester, the ethyl succinic acid diallyl, di-2-ethylhexyl fumarate, diethyl itaconate, the itaconic acid diisobutyl ester, diisooctyl citraconic acid and dimethyl citraconic acid; Polycarboxylate of aliphatic series is as 1,2-cyclohexane-carboxylic acid diethylester, 1,2-cyclohexane-carboxylic acid diisobutyl ester, tetrahydrophthalic acid diethylester and methyl bicycle (2,2,1) heptene-2,3-diethyl dicarboxylate; Aromatic multi-carboxy acid's ester, as the phthalic acid mono ethyl ester, repefral, the phthalic acid methyl ethyl ester, phthalic acid list isobutyl ester, diethyl phthalate, phthalic acid ethyl isobutyl ester, the positive butyl ester of phthalic acid list, phthalic acid ethyl n-butyl, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, heptyl phthalate ester, phthalic acid two-2-ethylhexyl, didecyl phthalate, benzyl butyl phthalate, the phthalic acid diphenyl, the naphthalene dicarboxylic acids diethylester, the naphthalene dicarboxylic acids dibutyl ester, 1,2,4-benzenetricarboxylic acid triethyl, 1,2,4-benzenetricarboxylic acid dibutyl ester; With the heterocycle polycarboxylate, as 3,4-furans dicarboxylic acids.

Other example that is included in the polycarboxylate in the titanium catalyst component is the long chain dicarboxylic acid ester, as diethylene adipate, diisobutyl adipate, diisopropyl sebacate, n-butyl sebacate, decanedioic acid caprylic acid and decanedioic acid two positive ethylhexyls.

In these polycarboxylates, preferably have those polycarboxylates of the skeleton that above-mentioned general formula represents.Be more preferably the malonate of the phthalic acid ester, maleate or the replacement that contain at least 2 carbon atom alcohols.Particularly preferably be the phthalic acid diester that contains at least 2 carbon atom alcohols.In the deposition electron donor, not necessarily always need be it as raw material, in the preparation process of titanium catalyst compound, can be transformed into the compound of this electronic donor compound capable, and the compound that can convert this electronic donor compound capable in preparation process to can use.

Another electron donor also can be present in the titanium catalyst component, but its amount must be seldom, because may produce otherwise impact too much.

The magnesium compound of use in titanium catalyst component (A) preparation is the magnesium compound that has reducing power or do not have reducing power.

Example with magnesium compound of reducing power comprises the magnesium compound that contains magnesium-carbon bond or magnesium-hydrogen bond, as dimethyl magnesium, magnesium ethide, dipropyl magnesium, dibutylmagnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethylmagnesium chloride, propyl group magnesium chloride, butylmagnesium chloride, hexyl magnesium chloride, amyl group magnesium chloride, butyl magnesium ethylate, ethyl-butyl magnesium and dibutyl magnesium hydride.Can use forming these magnesium compounds of complex compound with organo-aluminium, may be liquid or solid.The example that does not have the magnesium compound of reducing power comprises magnesium halide, as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; The alkoxyl magnesium halide is as methoxyl group chlorination magnesium, ethyoxyl magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride and octyloxy magnesium chloride; The aryloxy group magnesium halide is as phenoxy group magnesium chloride and methylphenoxy magnesium chloride; Alkoxyl magnesium is as magnesium ethylate, isopropoxy magnesium, butoxy magnesium, n-octyloxy magnesium and 2-ethyl hexyl oxy magnesium; Aryloxy group magnesium is as phenoxy group magnesium and dimethyl phenoxy magnesium; And magnesium carboxylates, as Magnesium dilaurate and dolomol.These magnesium compounds that do not have reducing power can be the compounds of being derived out by above-mentioned magnesium compound with reducing power, or above-mentionedly have also a compound that the magnesium compound of having the ability transforms in catalyst preparation process.Magnesium compound can be the complex compound with other metal, or with the mixture of other metallic compound, maybe may be the mixture of two or more these compounds.Preferred selection does not have the reducing power magnesium compound, and preferably halogen-containing magnesium compound.In above-mentioned all preferred magnesium compounds, magnesium chloride, alkoxy-magnesium chloride and aryloxymagnesium chloride are better.

Operational titanium compound is available various compound in solid titanium catalyst component (A) preparation process.In general, chemical formula is Ti(OR) _gX _4-gThe tetravalent titanium compound of (wherein R is an alkyl, and X is halogen atom and 0≤g≤4) is preferred.Concrete example comprises titanium tetrahalide, as tetrahydro titanium, titanium tetrabromide and titanium tetra iodide; Alkoxyl three halogenated titaniums are as methoxyl group titanium trichloride, ethyoxyl titanium trichloride, n-butoxy titanium trichloride, ethyoxyl titanium tribromide and isobutoxy titanium tribromide; Alkoxyl dihalide titanium is as methoxyl group titanium chloride, ethyoxyl titanium chloride, n-butoxy titanium chloride and ethyoxyl dibrominated titanium; Tri-alkoxy-halogenated titanium is as trimethoxy titanium chloride, ethyoxyl titanium chloride, n-butoxy titanium chloride and ethyoxyl titanium bromide and four alkoxytitaniums, as tetramethoxy titanium, purity titanium tetraethoxide and four titanium n-butoxide.In these compounds, Halogen titanium compound, particularly titanium tetrahalide are preferred.In above-mentioned all preferred compounds, with titanium tetrachloride for the most suitable.These titanium compounds can use separately or be used in combination, and also can use with hydrocarbon or halogenated hydrocarbons dilution back.

Titanium compound, magnesium compound and the electron donor that will deposit and the optional compound of use in titanium catalyst component (A) preparation process, as electron donor (for example, alcohol, phenol or monocarboxylic acid), the consumption of silicon compound or aluminium compound changes along with preparation method's change, usually uncertain, for example for every mole of magnesium compound, the amount that can use the electron donor of deposition is that 0.01 to 5 mole and electron donor are 0.01 to 500 mole.

In the present invention, use by titanium catalyst component (A), the catalytic component that organo-aluminum compound (B) and organo-silicon compound (C) are formed carries out polymerisation.

Component (B) can comprise as:

(ⅰ) in molecule, contain the organo-aluminum compound of one or more AL-C keys at least, as the organo-aluminum compound of following general formula,

R ¹mAl（OR ²）nH _pX _q

R wherein ¹And R ²Representative generally contains 1 to 15 the alkyl of carbon atom, preferably contains the alkyl of 1 to 4 carbon atom, not only can be identical but also can be different, and X represents halogen atom, and m, n, p and q represent 1 to 3 number separately, and m, n, p and q add up to 3.

(ⅱ) by formula M ' AlR ¹ ₄The alkylating complex compound of the aluminium of expression and the metal of I family, wherein M ' represents Li, Na or K, R ¹As defined above.

The example that falls into the organo-aluminum compound in above-mentioned (ⅰ) scope is that general formula is R ¹MAl(OR ²) _3-mCompound.

Wherein, R ¹And R ²As preceding definition, m preferably 1.5 to 3, and general formula is R ¹MAlX _3-mCompound, wherein, R ¹With X as previously mentioned, m is the number of 0＜m＜3 preferably.

General formula is R ¹MAlH _3-mCompound, R wherein ¹As preceding definition, m is 2 to 3 number.

With general formula be R ¹MAl(OR ²) nX _qCompound, R wherein ¹, R ²With X such as preceding definition, 0＜m≤3,0≤n＜30≤q＜3, m+n+q=3.

The object lesson of aluminium compound (ⅰ) comprises trialkylaluminium, as triethyl aluminum and tri-butyl aluminum; Trialkenyl aluminium is as three isopentene group aluminium; The dialkyl group aluminium alkoxide is as diethyl aluminium ethylate and dibutyl aluminium butoxide; Alkyl sesquialter aluminium alkoxide is as ethyl sesquialter aluminium ethylate and butyl sesquialter aluminium butoxide; Contain average group and become R ¹ _2.5Al(OR ²) _0.5Part alkoxylated alkyl group aluminium; The alkyl aluminum of part halo, dialkylaluminum halides for example is as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminium bromide; Alkyl sesquialter aluminum halide, as ethyl sesquialter aluminium chloride, butyl sesquialter aluminium chloride and ethyl sesquialter aluminium bromide; With alkyl dihalide aluminium, as ethylaluminum dichloride, propyl group al dichloride and butyl aluminum dibromide; Partially hydrogenated alkyl aluminum, dialkyl group aluminum hydride for example is as ADEH, dibutyl aluminum hydride; With the alkyl aluminum dihydride, as ethyl dihydroaluminium and propyl group aluminum dihydride; Alkyl aluminum such as ethyl ethyoxyl aluminium chloride, butyl butoxy aluminium chloride and ethyl ethyoxyl aluminium bromide with part alkoxylate and halogenation.

LiAl(C ₂H ₅) ₄And LiAl(C ₇H ₁₅) ₄May be as the object lesson of compound (ⅱ).

Also can enumerate the organo-aluminum compound as those examples of aluminium compound, wherein two or more aluminium atoms connect by oxygen atom or nitrogen-atoms, and (ⅰ) is similar with compound.Concrete example is (C ₂H ₅) ₂AloAl(C ₂H ₅) ₂, (C ₄H ₅) ₂AloAl(C ₄H ₉) ₂,

And MAO.

In these examples, the trialkylaluminium and the alkyl aluminum that are connected of two or more aluminium atoms wherein preferably.

Organo-silicon compound as catalytic component (C) are represented by following general formula (I):

RnSi（OR ¹） _4-n〔Ⅰ〕

Wherein R and R ¹Representation hydrocarbyl and 0＜n＜4.

The example of preferred R is alkyl, cycloalkyl, aryl, alkenyl, haloalkyl and aminoalkyl base, preferred R ¹Example be alkyl, cycloalkyl, aryl, alkenyl and alkoxyalkyl base, nR group and (4-n) R ¹Group may be identical or different separately.

The object lesson of organo-silicon compound (C) comprising:

The trimethyl methoxy silane, trimethylethoxysilane,

Dimethyldimethoxysil,ne, dimethyldiethoxysilane,

Diisopropyl dimethoxy silane,

Tert-butyl group methyl dimethoxysilane,

Tert-butyl group methyldiethoxysilane,

The tertiary pentyl methyldiethoxysilane,

Dimethoxydiphenylsilane,

Phenyl methyl dimethoxy silane,

The diphenyl diethoxy silane,

It is two-o-tolyl dimethoxy silane,

It is two-a tolyl dimethoxy silane,

It is two-p-methylphenyl dimethoxy silane,

It is two-the p-methylphenyl diethoxy silane,

It is two-ethylphenyl dimethoxy silane,

Dicyclohexyl dimethoxy silane,

Cyclohexyl methyl dimethoxy silane,

The cyclohexyl methyl diethoxy silane,

Ethyl trimethoxy silane,

Ethyl triethoxysilane,

Vinyltrimethoxy silane,

MTMS,

The n-pro-pyl triethoxysilane,

The decyl trimethoxy silane,

The decyl triethoxysilane,

Phenyltrimethoxysila,e,

γ-Lv Daibingjisanjiayangjiguiwan,

MTES,

Ethyl triethoxysilane,

VTES,

Tert-butyl group triethoxysilane,

Ne-butyltriethoxysilaneand,

The isobutyl group triethoxysilane,

Phenyl triethoxysilane,

γ-An Jibingjisanyiyangjiguiwan,

The chloro triethoxysilane,

Ethyl three isopropoxy silane,

Vinyl three butoxy silanes,

Cyclohexyl trimethoxy silane,

The cyclohexyl triethoxysilane,

2-norbornane trimethoxy silane,

2-norbornane triethoxysilane,

2-norbornane methyl dimethoxysilane,

Silester,

Butyl silicate,

Trimethyl phenoxysilane,

Methyl three allyloxy silane,

Vinyl three ('beta '-methoxy ethyoxyl) silane,

Vinyl triacetic acid base silane and

Dimethyl tetraethoxy disiloxane.

Preferably ethyl triethoxysilane in these compounds, the n-pro-pyl triethoxysilane, tert-butyl group triethoxysilane, VTES, phenyl triethoxysilane, vinyl three butoxy silanes, dimethoxydiphenylsilane, phenyl methyl dimethoxy silane, two-p-methylphenyl dimethoxy silane, right-the tolyl methyl dimethoxysilane, dicyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, 2-norbornane triethoxysilane, 2-norbornane methyl dimethoxysilane and diphenyl diethoxy silane.

The alpha-olefin that can be used for copolymerization of propylene may be ethene or the straight or branched alpha-olefin that contains 1 to 12 carbon atom.The preferred example of these alpha-olefins is ethene, butene-1, amylene-1, hexene-1,4-methylpentene-1, octene-1, isooctene-1 and decylene-1.

Before propylene polymerization or before propylene and the alpha-olefin copolymer, must carry out the prepolymerization of 3-methyl butene-1.

At titanium catalyst component (A), to small part organo-aluminum compound (B), and under the existence of organo-silicon compound (C), carry out prepolymerization, its consumption to every gram catalytic component (A) be about 0.1 to about 100 the gram, be preferably about 0.5 to about 50 grams, be more preferred from 0.5 to 20 gram, be preferably 1 to 20 gram especially.The amount of existing organo-aluminum compound (B) is for being enough to the above-mentioned required amount of 3-methyl butene-1 of the every gram component of polymerization (A), for example, be approximately 0.1 to 300 mole of in titanium catalyst component (A) every gram atom titanium, be preferably about 0.5 to about 100 moles, particularly preferred is about 1 to about 50 moles.

The amount of the organo-silicon compound of Cun Zaiing (C) is about 0.1 to about 100 moles to every gram atom titanium in solid titanium catalyst component (A) together, is preferably about 0.5 to about 20 moles, and particularly preferred is about 1 to about 10 moles.

Prepolymerization is preferably carried out in the unreactive hydrocarbons medium.Prepolymerization intermittently or carry out continuously, discontinuous method is the most effective because allow to use the catalyst concn more much higher in the discontinuous method than main polymerization reaction system, therefore preferred this method.

Calculate with the titanium atom of every liter of unreactive hydrocarbons medium, the concentration of suitable titanium catalyst component (A) is about 0.01 to about 200 mMs in pre-polymerization, is preferably about 0.05 to about 100 mMs.Temperature in the pre-polymerization process is preferably-20 to+80 ℃ approximately approximately usually at-20 to+100 ℃ approximately approximately, and the best is 0 to about 40 ℃.Carry out the prepolymerization reaction in the suspension of the catalyst to the atent solvent of the 3-methyl butene-1 by once adding or add continuously the amount of pre-determining.Molecular weight regulator such as hydrogen can add in pre-collecting process.

Use used catalyst and part organo-aluminum compound (B) and also do not have used organo-silicon compound (C) together in prepolymerization in pre-polymerization is with propylene polymerization or copolymerization.

In the method for the invention, the polymerization of propylene or combined polymerization are in gas phase or liquid phase or as carry out in slurry.In the slurry polymerization process, unreactive hydrocarbons can be used as solvent, or alkene itself also can be used as solvent.Calculate with the titanium atom in every liter of polymerization zone volume, the amount of the titanium catalyst component of use (A) 0.001 to about 0.5 mM, is preferably about 0.005 to about 0.5 mM for according to appointment.The amount of organo-aluminum compound (B) is to determine like this, and wherein the amount of metallic atom is about 1 to about 2000 moles to every mole titanium in the component in polymerization system (A) in the component (B), is preferably about 5 to about 500 moles.The amount of catalytic component (C) is calculated every mole titanium atom in component (A) with Si atom wherein and is about 0 to about 100 moles, is preferably about 1～50 mole that the best is about 3～20 moles.

Catalytic component (A), (B) and (C) can when polymerization, be in contact with one another, or before polymerization, contact.In the middle of the contact before polymerization, any two kinds of components can contact, or two or three part is in contact with one another.The contact of these catalytic components before polymerization can be carried out in inert gas atmosphere, or carries out in alkene atmosphere.

Polymerization temperature is preferable at about 20 to about 200 ℃, is more preferred from about 50 to about 100 ℃, polymerization pressure at atmospheric pressure to about 100 kilograms per centimeter ²In the scope, be preferably about 2 to about 50 kilograms per centimeter ²Polymerisation can adopt intermittently, semicontinuous or carry out continuously.In two steps or more multistep is carried out polymerization and also is fine per step reaction condition difference.The amount of the propylene of polymerization or propylene and alpha-olefin is 1000 to 100000 times that the 3-methyl butene-1 of polymerization in pre-polymerization is measured.Be preferably 1000 to 30000 times.

The present invention also comprises by simple tension at least and contains 1 to 1000 ppm by weight, is preferably 1 to 500 ppm by weight, is more preferred from 10 to 400 ppm by weight, the stretched polypropene film that the polypropylene of best 30 to 400 ppm by weight 3-methyl butenes-1 obtains.

Be used for preparing the polypropylene that stretched polypropene film of the present invention can contain the 3-methyl butene-1 of 1 to 1000 fen ppm by weight, can be as the polypropylene that obtains by the above-mentioned method of the present invention.

By at first using the polypropylene that described method is produced the polymer that contains 1000 ppm by weight 3-methyl butenes-1 at least, the polypropylene that contains 3-methyl butene-1 then and is not mediated, and also can obtain polypropylene.

The content of 3-methyl butene-1 polymer is 0.1%(weight at least in polypropylene), be preferably 0.1 to 50%(weight), the best is 0.5 to 10%(weight).Mediate temperature and can be preferably 180 to 250 ℃ at 140 to 350 ℃.The polypropylene that can be used for above-mentioned kneading can be Noblen or propylene and ethene or the copolymer that contains the alpha-olefin of 4 to 12 carbon atom straight chains or side chain.Other polymer, filler, stabilizing agent and other additive can mix in above-mentioned kneading operation.

By general known method, stretch as cross directional stretch, roll-in stretching or tubulose, at least simple tension contains 1 to 1000 ppm by weight, be preferably 10 to 300 ppm by weight, the polypropylene that is more preferred from the polymer of 30 to 150 ppm by weight 3-methyl butenes-1 can obtain stretched polypropene film of the present invention.

The present invention can provide has the high directionality index, the polypropylene of high catalytic efficiency and excellent transparency energy.Because the polypropylene of producing only contains the relict catalyst of minute quantity, therefore, removes the operation of relict catalyst and can omit, and in polyacrylic moulding, suppressed the corrosion of mould widely.

The present invention can also provide has the excellent transparency energy, the stretched polypropene film that the transparency and rigidity loss are reduced, it by the general at least the simple tension polypropylene that contains specified quantitative 3-methyl butene-1 polymer produce stretched polypropene film.

To illustrate the present invention in more detail by the following examples.

Embodiment 1

The preparation of titanium catalyst component (A)

Anhydrous magnesium chloride (7.14 grams, 75 mMs), 37.5 milliliters of decane and 35.1 milliliters of (225 mM) 2-Ethylhexyl Alcohols 130 ℃ of reactions 2 hours, are formed a uniform solution.Add 1.67 gram (11.3 mM) phthalic anhydrides in solution, by stirring mixture was stirred one hour at 130 ℃ subsequently, phthalic anhydride is dissolved in the uniform solution.Homogeneous solution cool to room temperature with generating remains on-20 ℃ and splashes in 200 milliliters of (1.8 moles) titanium tetrachlorides, and the dropping time, after dripping off, the intensification of experiencing 4 hours rose to 110 ℃ with the temperature of mixed solution in 1 hour.When temperature reaches 110 ℃, add 5.03 milliliters of (18.8 mM) isobutyl terephthalate.Mixture is stirred and kept under this temperature 2 hours, react after 2 hours, filter while hot, collect solid portion, and be suspended in 275 milliliters of tetrahydro titaniums.Suspension is 110 ℃ of reactions 2 hours, after reaction finishes, and solid collected by filtration part while hot, and fully wash at 110 ℃ with decane and hexane, till the titanium compound that in cleaning solution, dissociates.

Storage is by the synthetic solid titanium catalyst component (A) of said method.Wherein a part is dry forms to detect its catalyst.The result shows that the solid titanium catalyst component of generation (A) contains 2.6%(weight) titanium, 58%(weight) chlorine, 18%(weight) magnesium and 12.4%(weight) diisobutyl phthalate.

Prepolymerization

420 milliliters of pure hexanes are packed in 2 liters the autoclave of crossing with the nitrogen purge, be cooled to 0 ℃, with 50 mM triethyl aluminums, 10 gram 3-methyl butene-1,10 mM trimethyl methoxy silane and 5 mM titanium catalyst components (A) (calculating with titanium atom) add in the autoclave then.With after the autoclave sealing, under agitation in 20 ℃ with monomer polymerization 3 hours.After polymerization finishes, reactant mixture is taken out under blanket of nitrogen, remove the liquid part, separating solids part and make slurry in decane.The amount of pre-polymerization monomer is 0.9 gram to every gram catalyst.

Polymerization

100 liters of pure hexanes are packed in 250 liters the autoclave, and under propane atmosphere in room temperature with 94 mM triethyl aluminums, 9.4 living through the catalytic component (A) (calculating with titanium atom) of pre-polymerization, mM cyclohexyl methyl dimethoxy silane and 1.9 mMs add in the autoclave, after feeding 25NL hydrogen, with propylene 70 ℃ of polymerizations 2 hours.Between polymerization period, pressure maintains 7 kilograms per centimeter ²Gauge pressure.

After polymerization finished, filtration contained the slurry that generates polymer, and it is separated into white powder shaped polymer and liquid part.After the drying, the white powder shaped polymer is 57.9 kilograms.This polymer with boiling pentane extracting after residue be 98.8%, MFR is 2.6 fens Grams Per Minutes, apparent density is 0.46 grams per milliliter.

In view of such fact, separating part titanium during prepolymerization, polymerization 14900 gram propylene (every gram catalyst).Therefore, the content of poly-(3-methyl butene-1) is 60 ppm by weight.

The preparation of biaxially drawn films

Polypropylene that contains poly-(3-methyl butene-1) and 0.1 weight fraction calcium stearate with the generation of 100 weight fraction, 0.1 weight fraction BHT(2, the 6-di-tert-butyl hydroxy toluene) and 0.1 weight fraction Irganox 1010(by Ciba-Geigy) antioxidant produced, four (methylene-3(3 ', 5 '-the di-t-butyl hydroxyphenyl) propionic ester)-methane) mix in the Henschel blender with used as stabilizers, subsequently, utilization has the extruding machine of 65 millimeters body diameters, mediates temperature at 220 ℃ and carries out granulation.

Utilizing body diameter is the particle that 90 millimeters sheet extrusion machine is made at 280 ℃ of extrusion moldings, by the sheet material of making 1.5 millimeters thick at 30 ℃ cold roller.Utilize the continuous biaxial stretching device of tentering formula, 145 ℃ with five times of the sheet material longitudinal stretchings that obtain, subsequently in stenter in 10 times of 170 ℃ of cross directional stretch, obtain the biaxially drawn films of about 20 micron thickness.

The evaluation of film

The transparency of film is represented with the mist degree and the gloss of front.Sometimes, because the variation or the difference of the light that causes in the slickness of film surface, these performances and visualization inconsistent.In this application, the transparency is determined by haze value (the smaller the better), is determined by visualization as the properties of transparency of optical property.

(1) uses the visual valuation properties of transparency

Five films (every thick 30 microns) are stacked together to be examined through the light of film from fluorescent lamp, and properties of transparency is estimated with 5 grades, and wherein 5 is good, and 1 is bad.

(2) light scattering index (LST) is by Toyo seiki co, and the LSI test machine that Lts makes is measured.

(3) mist degree is measured according to ASTMD1003.

(4) spherocrystal diameter.

The diameter of spherocrystal is measured by stereoscope (X100) in the sheet material cross section before biaxial stretching.

The spherulite size of sheet material is more little, and the properties of transparency of biaxially drawn films will be good more.Therefore, just can use through measuring the spherocrystal diameter to obtain having good clear performance film.

(5) Young's modulus

According to JISK6781,, utilize the horizontal Young's modulus of Instron tensile tester MEASUREMENTS OF THIN 50 meters/minute of the speed of pulling out.

Embodiment 2

The preparation of titanium catalyst component (A)

As described in embodiment 1, the Ti catalytic component (A) of preparation stands prepolymerization subsequently.

Prepolymerization

Pure n-decane (1330 milliliters) is added in 2 liters the autoclave of crossing with the nitrogen purge, be cooled to 0 ℃, subsequently, add 150 mM triethyl aluminums to autoclave, 60 gram 3-methyl butene-1,150 mM trimethyl methoxy silane and 15 mM titanium catalyst components (A) (in titanium atom).After treating the autoclave sealed air-tight, under agitation with monomer in 20 ℃ of polyase 13s hour.After polymerization finishes, take out reactant mixture, remove the liquid part, isolate solid portion, and in decane, make slurry.The amount of pre-polymerization monomer is 1.8 grams to every gram catalyst.

The polymerization of propylene

Pure n-decane (2.8 liters) is added in the glass reactor of crossing with the abundant purge of nitrogen that agitator is housed (5 liters).Treat that temperature rises to 60 ℃, subsequently with propylene and hydrogen (hydrogen content 0.83%(volume)) admixture of gas feed in the n-decane in the bubbling mode, when feeding admixture of gas, add 120 mM triethyl aluminums, 12 mM cyclohexyl methyl dimethoxy silane and 2.37 mM titanium catalyst components (A) (in titanium atom), propylene was 60 ℃ of polymerizations 2.5 hours.Add the beginning interval after 2.5 hours from catalyst, add about 5 milliliters of isopropyl alcohols, stop polymerisation, use nitrogen alternative feeds gas simultaneously.Filtration contains the n-decane suspension that generates polymer, and solid polymer fully washs with n-hexane, and under reduced pressure 80 ℃ of dryings.The amount that generates polymer is 1003 grams, and the melt index of polymer is 8.5 grams/10 minutes, and therefore, poly-(3-methyl butene-1) content in the polymer is 1.0%(weight).

The preparation of biaxially drawn films

The generation polymer that will contain poly-(3-methyl butene-1) (1.0 weight fraction), 0.1 weight fraction calcium stearate, 0.1 weight fraction BHT and add in the 100 weight fraction polypropylene as 0.1 fen Irganox 1010 of stabilizing agent, this polyacrylic II (pentane extracting residue) be 97.2% and MFR be 1.59 grams/10 minutes.Under the condition identical, with mixture pelleting and make sheet material with embodiment 1.Under the condition identical,, obtain the biaxially drawn films of about 20 micron thickness with the sheet material biaxial stretching with embodiment 1.

Comparative example 1

The preparation of titanium catalyst component (A)

With with embodiment 1 in same method prepare titanium catalyst component (A).

Prepolymerization

Pure hexane (420 milliliters) added to cross volume with purging with nitrogen gas be in 2 liters the autoclave, and be cooled to 0 ℃, subsequently, in autoclave, add 50 mM triethyl aluminums, 50 gram 3-methyl butene-1,10 mM trimethyl methoxy silane and 5 mM titanium catalyst components (A) (in titanium atom).After treating that autoclave sealing is air tight, under agitation with monomer 20 ℃ of polymerizations 6 hours, after polymerization finishes, under blanket of nitrogen, take out reactant mixture, remove the liquid part, the segregation solid portion is also made slurry in decane.The amount of pre-polymerization monomer is 4.1 grams to every gram catalyst.

Polymerization

In the autoclave with 250 liters of pure decane (100 liters) addings, and add 300 mM triethyl aluminums under room temperature propylene atmosphere, 30 mM cyclohexyl methyl dimethoxy silane and 6 mMs are through pre-polymerized catalyst components (A) (in titanium atom).After feeding 25NL hydrogen, temperature is risen to 70 ℃, with propylene polymerization 30 minutes.Pressure maintains 7 kilograms per centimeter between polymerization period ²Gauge pressure.

After polymerization finished, filtration contained the slurry that generates polymer, is separated into white powder shaped polymer and liquid part.The amount of the white powder shaped polymer that dry back generates is 43.4 kilograms.Polymer is 98.8% with boiling n-heptane extracting residue, and MFR is 2.8 fens Grams Per Minutes, and apparent density is 0.43 grams per milliliter.

In view of such fact, separated portions Ti is to every gram catalyst polymerizable 3.540 gram propylene during pre-polymerization.Therefore, the content of poly-(the 3-methyl butene-1) of the polymer of generation is 1200 ppm by weight.

The preparation of biaxially drawn films

The polypropylene and the 0.1 weight fraction calcium stearate that 100 weight fraction are contained the generation of poly-(3-methyl butene-1), 0.1 weight fraction BHT and mix as 0.1 weight fraction Irganox 1010 of stabilizing agent, subsequently, under the condition identical, carry out granulation with embodiment 1, make sheet material biaxial stretching again, provide biaxially drawn films with 30 micron thickness.

Comparative example 2

The preparation of biaxially drawn films

(having II (pentane extracting residue) is 97.2% with 100 weight portion polypropylene powders, MFR is 1.5 grams/10 minutes) mix with 0.1 weight fraction calcium stearate, 0.1 weight fraction BHT and 0.1 weight fraction Irganox 1010, subsequently with mixture pelleting, make sheet material biaxial stretching again, provide biaxially drawn films with 30 micron thickness.

The results are shown in table 1 what embodiment 1,2 and comparative example 1,2 obtained.

Claims (5)

1, stretched polypropene film, this film are to stretch at least one direction by the polypropylene to 3-methyl butene-1 polymer that contains 1 to 1000 ppm by weight to obtain, and described polypropylene is:

(1) mixture of kneading of following material:

(i) a kind of acrylic polymers, it is to be polymerized in the presence of 3-methyl butene-1 prepolymer of 1000ppm (weight) at least, described prepolymer has the catalyst prepolymerization that following component forms and forms; (A) contain magnesium, titanium, halogen and polycarboxylate solid titanium catalyst component as basis; (B) organo-aluminum compound; (C) by general formula R nSi (OR ¹) _4-aThe organo-silicon compound of representative, wherein R and R ¹Identical or inequality, and representation hydrocarbyl, n be greater than 0, less than 4, with

The acrylic polymers that does not (ii) contain 3-methyl butene-1; Or:

(2) a kind of acrylic polymers, it is to be polymerized containing in the presence of 3-methyl butene-1 prepolymer of 1-1000ppm (weight), described prepolymer is that prepolymerization forms in the presence of the catalyst of above-mentioned containing (A), (B), (C).

2, according to the film of claim 1, the content of 3-methyl butene-1 polymer in the wherein said polypropylene is 1 to 500 ppm by weight.

3, according to the film of claim 1, the content of 3-methyl butene-1 polymer in the wherein said polypropylene is 10 to 400 ppm by weight.

4, according to the film of claim 1, wherein said stretching adopts cross directional stretch method, roll-in pulling method or tubulose pulling method to carry out.

5, according to the film of claim 4, wherein said stretching is to stretching along twin shaft.